Acid azo dyes from a 3-amino-benzisothiazole-[2,1]-5-sulfonic acid diazo component

ABSTRACT

Acid monoazo dyes of the formula ##STR1## in which X is hydrogen, chloro, bromo, nitro, C 1  to C 4  alkyl, methoxy, ethoxy or C 2  to C 4  alkanoylamino and K is a radical of a coupling compound as defined below. The dyes are suitable for dyeing natural or synthetic polyamides giving colorations with very good fastness properties.

This is a continuation, of application Ser. No. 757,431, filed Jan. 6, 1977 now abandoned.

The invention relates to compounds which in the form of the free acids have the formula (I): ##STR2## in which X is hydrogen, chloro, bromo, nitro, C₁ to C₄ alkyl, methoxy, ethoxy or NHCO-alkyl, the alkyl being C₁ to C₄ ;

K is a radical of the formula: ##STR3## R¹ is hydrogen, chloro, methyl, methoxy or ethoxy; R² is hydrogen, chloro, methyl, ethyl, benzyl, sulfobenzyl, methoxy, ethoxy, carboxy, NHCO-(C₁ to C₄ alkyl), NHCOCH₂ Cl, NHCOCHCl₂, NHCONH₂ or SO₃ H;

R³ is hydrogen, C₁ to C₄ alkyl, C₂ or C₃ hydroxyalkyl or dihydroxyalkyl, β-sulfoethyl, γ-sulfopropyl, β-cyanoethyl, β-hydroxy-γ-chloropropyl, C₁ to C₄ alkoxyethyl, acetoxyethyl, β-chloroethyl, γ-aminopropyl, γ-acetylaminopropyl, β-carboxyethyl, β-carbamoylethyl, benzyl, sulfobenzyl, phenylethyl, sulfophenylethyl or cyclohexyl;

R⁴ is C₁ to C₄ alkyl, C₂ or C₃ hydroxyalkyl, β-cyanoethyl, β-chloroethyl, C₁ to C₄ alkoxyethyl, benzyl or sulfobenzyl;

R⁵ is amino, acetylamino, chloroacetylamino, phenoxyacetylamino, benzoylamino, chlorobenzoylamino or dichlorobenzoylamino;

R⁶ is methyl, chloromethyl, phenyl, chlorophenyl or acetylamino;

R⁷ is C₁ to C₈ alkyl, C₂ or C₃ hydroxyalkyl, phenyl-(C₁ to C₄ alkyl), cyclohexyl or phenyl;

R⁸ is hydrogen, chloro, methyl, methoxy or hydroxysulfonyl;

m is zero, 1 or 2; and

n is 1 or 2.

Examples of individual radicals X in addition to those already specified are: CH₃, C₂ H₅, C₃ H₇, C₄ H₉, NHCOCH₃, NHCOC₂ H₅, NHCOC₃ H₇ and NHCOC₄ H₉.

Examples of individual alkyl and alkoxyalkyl radicals for R³ and R⁴ are: CH₃, C₂ H₅, C₃ H₇, C₄ H₉, C₂ H₄ OCH₃, C₂ H₄ OC₂ H₅, C₂ H₄ OC₃ H₇ and C₂ H₄ OC₄ H₉.

Examples of R⁷ in addition to those already specified are: CH₃, C₂ H₅, C₃ H₇, C₄ H₉, C₅ H₁₁, C₆ H₁₃, C₈ H₁₇, ##STR4## C₆ H₅ CH₂, C₆ H₅ C₂ H₄, ##STR5## C₆ H₅ C₃ H₆ and C₆ H₅ C₄ H₈.

Compounds of the formula (I) may be prepared by reacting a diazo compound of an amine of the formula (II): ##STR6## with a coupling component of the formula (III):

    HK                                                         (III)

in which X and K have the meanings given above.

Particular industrial importance attaches to compounds of the formula (Ia): ##STR7## in which X¹ is hydrogen, chloro or bromo; and

K¹ is a radical of the formula ##STR8##

Preferred radicals are therefore:

for R² hydrogen, methyl, chloro, acetylamino or SO₃ H;

for R³ and R⁴ C₁ to C₄ alkyl, C₂ H₄ OH, CH₂ CHOHCH₃, CH₂ CHOHCH₂ OH, CH₂ --CH₂ --OCOCH₃, CH₂ CH₂ Cl, CH₂ CH₂ CN, CH₂ CHOHCH₂ Cl, CH₂ CH₂ OCH₃, C₂ H₄ OC₂ H₅, C₃ H₆ NHCOCH₃ or CH₂ C₆ H₄ SO₃ H; and for R¹ hydrogen, methoxy or methyl.

Dyes of the formula (I) are red to greenish blue and are particularly suitable for the coloration of natural and synthetic polyamides such as wool, nylon-6, nylon-6,6 and furs.

Dyeings are obtained having very good fastness properties of which fastness to light and wet treatments such as fastness to washing, water, perspiration, fulling and sea water are to be emphasized. The dyes moreover have a very high color strength. In the case of fur dyeing the dyes have good fastness to hot pressing and can be combined to produce brown and black shades.

The following Examples illustrate the invention. The parts and percentages are by weight unless otherwise stated.

EXAMPLE 1

23 parts of 3-aminobenzoisothiazole-5-sulfonic acid is dissolved in 200 parts of water with 4.8 parts of caustic soda, a solution of 6.9 parts of sodium nitrite in water is added and the whole is dripped into a mixture of 200 parts of ice and 46.4 parts of 32% hydrochloric acid while stirring. The suspension of the diazonium salt is stirred for about one hour at 0° to 5° C. and then the excess of nitrite is destroyed with a small amount of sulfamic acid. A solution of 21.63 parts of 3-(N,N-diethylamino)-acetylaminobenzene in 100 parts of water and 11.6 parts of 32% hydrochloric acid is added. After the whole has been stirred for about fifteen minutes the pH is adjusted to 4 to 5 with a solution of 57.5 parts of sodium acetate. The reaction mixture is further stirred until coupling is completed and the dye is then suction filtered and dried at 70° C. at subatmospheric pressure. A dark powder is obtained having the formula: ##STR9## It is soluble in water to give a reddish blue color and gives reddish blue dyeings of good fastness properties on nylon 6, furs, wool and leather.

Dyes having similar tinctorial properties and set out in the following Table are prepared analogously to Example 1.

    __________________________________________________________________________     No.                                                                               Diazo component                                                                          Coupling component                                                                               Hue on nylon 6                                  __________________________________________________________________________         ##STR10##                                                                                ##STR11##        blue                                            3  "                                                                                         ##STR12##        blue                                            4  "                                                                                         ##STR13##        reddish blue                                    5  "                                                                                         ##STR14##        reddish blue                                    6  "                                                                                         ##STR15##        reddish blue                                    7  "                                                                                         ##STR16##        reddish blue                                    8  "                                                                                         ##STR17##        reddish blue                                    9  "                                                                                         ##STR18##        reddish blue                                    10 "                                                                                         ##STR19##        blue                                            11 "                                                                                         ##STR20##        reddish blue                                    12 "                                                                                         ##STR21##        reddish blue                                    13 "                                                                                         ##STR22##        blue                                            14 "                                                                                         ##STR23##        reddish blue                                    15 "                                                                                         ##STR24##        reddish blue                                    16 "                                                                                         ##STR25##        blue                                            17 "                                                                                         ##STR26##        reddish blue                                    18 "                                                                                         ##STR27##        violet                                          19 "                                                                                         ##STR28##        violet                                          20 "                                                                                         ##STR29##        reddish blue                                    21 "                                                                                         ##STR30##        violet                                          22 "                                                                                         ##STR31##        violet                                          23 "                                                                                         ##STR32##        reddish blue                                    24 "                                                                                         ##STR33##        reddish blue                                    25 "                                                                                         ##STR34##        reddish blue                                    26 "                                                                                         ##STR35##        violet                                          27 "                                                                                         ##STR36##        greenish blue                                   28 "                                                                                         ##STR37##        dark blue                                       29 "                                                                                         ##STR38##        red                                             __________________________________________________________________________

EXAMPLE 30

23 parts of 3-aminobenzoisothiazole-5-sulfonic acid is diazotized analogously to Example 1. A neutral solution of 24 parts of 3-(N,N-diethylamino)-benzenesulfonic acid in 100 parts of water is then added to the suspension of the diazonium salt. The mixture is then adjusted to a pH of 4 to 5 with sodium acetate and further stirred until the coupling is ended. The dye of the composition: ##STR39## is salted out with 160 parts of sodium chloride, suction filtered and dried at 70° C. It dyes nylon 6, wool and fur fast reddish blue shades.

The dyes collected in the following Table may be prepared as described in Example 30; the coupling components of Examples 31 to 40 are dissolved in dilute hydrochloric acid.

    __________________________________________________________________________     No.                                                                               Diazo component                                                                          Coupling component Hue on nylon 6                                 __________________________________________________________________________     31                                                                                 ##STR40##                                                                                ##STR41##         reddish blue                                   32 "                                                                                         ##STR42##         reddish blue                                   33 "                                                                                         ##STR43##         reddish blue                                   34 "                                                                                         ##STR44##         violet                                         35 "                                                                                         ##STR45##         reddish blue                                   36 "                                                                                         ##STR46##         reddish blue                                   37 "                                                                                         ##STR47##         violet                                         38 "                                                                                         ##STR48##         reddish blue                                   39 "                                                                                         ##STR49##         reddish blue                                   40 "                                                                                         ##STR50##         reddish blue                                   41 "                                                                                         ##STR51##         reddish blue                                   42 "                                                                                         ##STR52##         reddish blue                                   43 "                                                                                         ##STR53##         greenish blue                                  44 "                                                                                         ##STR54##         greenish blue                                  45 "                                                                                         ##STR55##         reddish blue                                   46 "                                                                                         ##STR56##         reddish blue                                   47 "                                                                                         ##STR57##         blue                                           48 "                                                                                         ##STR58##         reddish blue                                   49 "                                                                                         ##STR59##         reddish blue                                   50 "                                                                                         ##STR60##         blue                                           51 "                                                                                         ##STR61##         blue                                           52 "                                                                                         ##STR62##         reddish blue                                   53 "                                                                                         ##STR63##         blue                                           54 "                                                                                         ##STR64##         reddish dark blue                              55 "                                                                                         ##STR65##         violet                                         56 "                                                                                         ##STR66##         reddish blue                                   57 "                                                                                         ##STR67##         reddish blue                                   58 "                                                                                         ##STR68##         reddish blue                                   __________________________________________________________________________

EXAMPLE 59

23 parts of 3-aminobenzoisothiazole-5-sulfonic acid is diazotized as described in Example 1 and an aqueous solution of 25 parts of 3-(N,N-dihydroxyethylamino)-acetylaminobenzene is added to the suspension of the diazonium salt. After coupling has taken place the dye solution is evaporated to dryness. The powder obtained which has the formula: ##STR69## dyes nylon 6, wool and fur clear and fast dark blue hues.

The dyes comprised within the following Table may be prepared according to Example 59.

    __________________________________________________________________________     No.                                                                               Diazo component                                                                           Coupling component                                                                              Hue on nylon 6                                  __________________________________________________________________________     60                                                                                 ##STR70##                                                                                 ##STR71##       reddish blue                                    61 "                                                                                          ##STR72##       reddish blue                                    62 "                                                                                          ##STR73##       violet                                          63 "                                                                                          ##STR74##       reddish blue                                    64 "                                                                                          ##STR75##       blue                                            65 "                                                                                          ##STR76##       dark blue                                       66 "                                                                                          ##STR77##       reddish blue                                    67 "                                                                                          ##STR78##       reddish blue                                    68 "                                                                                          ##STR79##       reddish blue                                    69 "                                                                                          ##STR80##       violet                                          __________________________________________________________________________     The following dyes are also obtained analogously to Example 1:                 No.                                                                               Diazo component                                                                           Coupling component                                                                              Hue on nylon 6                                  __________________________________________________________________________     70*                                                                                ##STR81##                                                                                 ##STR82##       blue                                            71*                                                                               "                                                                                          ##STR83##       reddish blue                                    72*                                                                               "                                                                                          ##STR84##       reddish blue                                    73*                                                                               "                                                                                          ##STR85##       reddish blue                                    __________________________________________________________________________      *The coupling components are dissolved in the necessary amount of acetone                                                                               

The following dyes may be prepared analogously to Example 30:

    __________________________________________________________________________     No.                                                                               Diazo component                                                                           Coupling component                                                                               Hue on nylon 6                                 __________________________________________________________________________     74                                                                                 ##STR86## CH.sub.3 COCH.sub.2 CONHC.sub.6 H.sub.5                                                          red                                            75 "                                                                                          ##STR87##        red                                            76 "                                                                                          ##STR88##        red                                            77 "                                                                                          ##STR89##        red                                            78 "                                                                                          ##STR90##        red                                            79 "                                                                                          ##STR91##        red                                            80 "                                                                                          ##STR92##        red                                            81 "                                                                                          ##STR93##        bluish red                                     82 "                                                                                          ##STR94##        bluish red                                     83 "                                                                                          ##STR95##        bluish red                                     84 "                                                                                          ##STR96##        bluish red                                     __________________________________________________________________________ 

We claim:
 1. An acid dye which in the form of the free acid has the formula ##STR97## wherein: X is hydrogen, chloro, bromo, nitro, C₁ - to C₄ -alkyl, methoxy, ethoxy or NHCO-(C₁ to C₄ -alkyl)R¹ is hydrogen, chloro, methyl, methoxy or ethoxy.
 2. A dye as set forth in claim 1 of the formula: ##STR98##
 3. A dye as set forth in claim 1 wherein R¹ is hydrogen, methoxy or methyl.
 4. A dye as set forth in claim 1 which in the form of free acid has the formula: ##STR99## wherein: X¹ is hydrogen, chloro or bromo.
 5. A dye as set forth in claim 1 wherein R¹ is methoxy.
 6. A dye as set forth in claim 1 wherein R¹ is methyl.
 7. A dye as set forth in claim 1 wherein R¹ is hydrogen. 